Proton Conductivity Enhancement at High Temperature on Polybenzimidazole Membrane Electrolyte with Acid-Functionalized Graphene Oxide Fillers.

Graphene oxide (GO) and its acid-functionalized form are known to be effective in enhancing the proton transport properties of phosphoric-acid doped polybenzimidazole (PA-doped PBI) membranes utilized in high-temperature proton exchange membrane fuel cells (HTPEMFC) owing to the presence of proton-conducting functional groups. This work aims to provide a comparison between the different effects of GO with the sulfonated GO (SGO) and phosphonated GO (PGO) on the properties of PA-doped PBI, with emphasis given on proton conductivity to understand which functional groups are suitable for proton transfer under high temperature and anhydrous conditions. Each filler was synthesized following existing methods and introduced into PBI at loadings of 0.25, 0.5, and 1 wt.%. Characterizations were carried out on the overall thermal stability, acid doping level (ADL), dimensional swelling, and proton conductivity. SGO and PGO-containing PBI exhibit better conductivity than those with GO at 180 °C under anhydrous conditions, despite a slight reduction in ADL. PBI with 0.5 wt.% SGO exhibits the highest conductivity at 23.8 mS/cm, followed by PBI with 0.5 wt.% PGO at 19.6 mS/cm. However, the membrane with PGO required a smaller activation energy for proton conduction, thus less energy was needed to initiate fast proton transfer. Additionally, the PGO-containing membrane also displayed an advantage in its thermal stability aspect. Therefore, considering these properties, it is shown that PGO is a potential filler for improving PBI properties for HTPEMFC applications.